US10696560B2ActiveUtilityPatentIndex 37
Small crystal EMM-17, its method of making and use
Est. expiryJul 27, 2037(~11.1 yrs left)· nominal 20-yr term from priority
Inventors:JOHNSON IVY DHRYCENKO NADYA ADATZ THEODORE ELONERGAN WILLIAM WSTROHMAIER KARL GVROMAN HILDA BGALLOW KEITH CWESTON SIMON C
B01J 20/18C01B 39/08C10G 29/205C01P 2002/72B01J 29/70C10G 25/03B01J 29/40C01P 2004/62C10G 47/16C01B 37/007C01B 37/02C10G 11/05C01P 2006/12C01B 39/48
37
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Claims
Abstract
A molecular sieve material, EMM-17, has in its as-calcined form, a total surface area of greater than 550 m2/g and/or an external surface area of greater than about 100 m2/g as measured by the BET Method, and a specific X-ray diffraction pattern.
Claims
exact text as granted — not AI-modifiedThe invention claimed is:
1. A crystalline molecular sieve material having, in its as-synthesized form, a particle size of less than 1.0 micron as measured by SEM, and an X-ray diffraction pattern including the following peaks in Table 2:
TABLE 2
d-spacing
Relative Intensity
(Å)
[100 × I/I(o)] %
17.3-16.4
1-10
11.8-11.3
60-100
11.1-10.7
60-100
10.7-10.3
30-100
8.58-8.34
30-80
4.21-4.15
10-40
4.17-4.11
5-30
4.07-4.01
10-40
3.951-3.899
60-100
3.922-3.871
10-40
3.832-3.784
50-90
3.737-3.691
10-40
3.704-3.659
10-40
3.677-3.632
5-30
3.537-3.496
10-40
2.077-2.063
5-30.
2. The crystalline molecular sieve material of claim 1 having a composition comprising the molar relationship:
k F: m Q:( n )YO 2 :X 2 O 3 ,
wherein 0≤k≤1.0, 0<m≤1.0, n is at least 30, F is a source of fluoride, Q is an organic structure directing agent, X is a trivalent element and Y is a tetravalent element.
3. The crystalline molecular sieve material of claim 2 , wherein X includes one or more of B, Al, Fe, and Ga and Y includes one or more of Si, Ge, Sn, Ti, and Zr.
4. The crystalline molecular sieve material of claim 2 , wherein X is aluminum and Y is silicon.
5. The crystalline molecular sieve material of claim 2 , wherein Q is selected from the group consisting of 1-methyl-4-(pyrrolidin-1-yl)pyridinium cations, 1-ethyl-4-(pyrrolidin-1-yl)pyridinium cations, 1-propyl-4-(pyrrolidin-1-yl)pyridinium cations, 1-butyl-4-(pyrrolidin-1-yl)pyridinium cations and mixtures thereof.
6. A crystalline molecular sieve material having, in its as-calcined form, a total surface area of greater than 550 m 2 /g and/or an external surface area of greater than 100 m 2 /g as measured by the BET Method, and an X-ray diffraction pattern including the following peaks in Table 1:
TABLE 1
d-spacing
Relative Intensity
(Å)
[100 × I/I(o)] %
17.4-16.4
1-10
12.6-12.1
1-20
11.8-11.4
60-100
11.2-10.8
5-30
10.7-10.3
30-80
8.62-8.38
10-40
6.09-5.96
1-20
5.71-5.61
1-20
4.23-4.17
1-20
4.09-4.03
1-10
3.952-3.901
10-40
3.857-3.809
5-30
3.751-3.705
1-20
3.727-3.682
1-20
3.689-3.644
1-10
3.547-3.506
1-20.
7. The crystalline molecular sieve material of claim 6 and having a composition comprising the molar relationship:
( n )YO 2 :X 2 O 3 ,
wherein n is at least 30, X is a trivalent element, and Y is a tetravalent element.
8. The crystalline molecular sieve material of claim 7 , wherein X includes one or more of B, Al, Fe, and Ga and Y includes one or more of Si, Ge, Sn, Ti, and Zr.
9. The crystalline molecular sieve material of claim 7 , wherein X is aluminum and Y is silicon.
10. The crystalline molecular sieve material of claim 6 , wherein the ratio of the external surface area to the total surface area of said as-calcined crystalline molecular sieve is greater than or equal to 0.35 as measured by the BET Method.
11. A method of making said crystalline molecular sieve material of claim 6 , the method comprising the steps of:
(a) preparing a synthesis mixture capable of forming said material, said mixture comprising water (H 2 O), a source of hydroxyl ions (OH − ), a source of an oxide of a tetravalent element (Y), optionally a source of a trivalent element (X), optionally a source of said fluoride ions (F − ), and said organic structure directing agent (Q), wherein said synthesis mixture has a composition, in terms of mole ratios, in the following amounts and/or ranges:
YO 2 /X 2 O 3
at least 30;
H 2 O/YO 2
2 to 100, or 4 to 50;
OH − /YO 2
0.1 to 1;
F/YO 2
0 to 1; and
Q/YO 2
0.1 to 1;
(b) removing water from said synthesis mixture under suitable freeze drying conditions to form a free-flowing powder of said synthesis mixture, said free-flowing powder having a H 2 O/SiO 2 molar ratio of less than 10;
(c) heating and optionally mixing said free-flowing powder of said synthesis mixture under crystallization conditions until said crystalline molecular sieve material is formed.
12. The method of claim 11 , wherein said suitable freeze drying conditions of step (b) include a temperature between −200° C. and 0° C. and a vacuum pressure less than 760 torr (101.3 kPa).
13. The method of claim 11 , wherein step (c) comprises both heating and mixing said free-flowing powder of said synthesis mixture.
14. The method of claim 11 , wherein said step (b) includes grinding the freeze-dried synthesis mixture to form said free-flowing powder.
15. The method of making said crystalline molecular sieve material of claim 11 , wherein water (H 2 O) is added to said free-flowing powder of said synthesis mixture so that said H 2 O/YO 2 molar ratio in the range of 1 to 10.
16. The method of claim 11 , wherein step (c) includes mixing under a cataracting mixing regime.
17. The method of claim 16 , wherein said step (c) is conducted in a ploughshare-type mixer.
18. The method of claim 11 , wherein said crystallization conditions include a temperature in the range of 100° C. to 250° C.
19. The method of claim 11 , wherein said source of fluoride (F) ions is one or more of HF, NH 4 F, and NH 4 HF 2 .
20. The method of claim 11 , further comprising the steps of:
(d) recovering said crystalline molecular sieve material from step (c);
(e) calcining said crystalline molecular sieve material to remove the organic structure directing agent (Q) to form said crystalline molecular sieve material in as-calcined form.
21. The method of claim 20 , further comprising the step of:
(f) ion-exchanging said crystalline molecular sieve material in as-calcined form with an ammonium salt.
22. An adsorbent comprising a crystalline molecular sieve material of claim 1 or a crystalline molecular sieve material made by the method of claim 21 .
23. A process for converting a feedstock comprising an organic compound to a conversion product which comprises contacting said feedstock at organic compound conversion conditions with a catalyst, said catalyst comprising an active form of a crystalline molecular sieve material of claim 1 or a crystalline molecular sieve material made by the method of claim 20 .Cited by (0)
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